Composition and method for acidizing earthen formations

ABSTRACT

A formation is acidized with a composition comprising a formation acidizing acid and a cationic surfactant which renders oil-containing earthen formations oil-wet, said surfactant being present in said composition in an amount which is sufficient to increase the reaction time of the acid acting on the formation.

Umted States Patent 11 1 1111 3,

Crowe Nov. 4, 1975 COMPOSITION AND METHOD FOR 3,113,113 12/1963 Marsh et a1. 252/855 0 ACIDIZING EARTHEN FORMATIONS 3,205,169 9/19/65 3,319,714 5/1967 [75] Inventor: Curtis W. Crowe, Tulsa, Okla. 333L179 5 3 3,404,094 10/1968 [73] Asslgnee' 3:33;: g gg 3,434,545 3/1969 Bombardieri 166/307 [22] Filed: Dec. 18, 1972 Primary Examiner -Benjamin R. Padgett Assistant ExaminerB. H. Hunt 21 l. N .z 1 App 0 3l6421 Attorney, Agent, or Firm-Bruce M. Kanuch [52] US. Cl 252/855 C; 16660225152350? [57] ABSTRACT [51] Int. Cl? E21B 43/28 A formation is acidized with composition comprising 58 Field of Search 166/307; 252/855 (3 a formation acidiling acid and a Cationic Surfactant which renders oil-containing earthen formations oil- [56 References Cited wet, said surfactant being present in said composition UNITED STATES PATENTS in an amount which is sufficient to increase the reac- 2 331 594 10,1943 B] 252/8 55 D tion time of the acid acting on the formation.

all 2,908,643 10/1959 Thompson et a1. 252/855 D 20 Claims, N0 Drawings COMPOSITION AND METHOD FOR ACIDIZHNG EARTHEN FORMATIONS BACKGROUND OF THE INVENTION It is oftentimes desirable to increase the distance into a wellbore or earth formation in which an acidizing solution can act on the formation before it becomes spent, i.e., it is desirable to increase the reaction time of the acid.

Various methods have been utilized to increase the reaction time of various acidizing solutions on acidizable formations. For example, in some instances an emulsion is prepared containing an oil external phase and an acid internal phase. The oil separates the acid from the formation rock and thereby extends the distance into the formation that the emulsion can pene trate before the acid becomes spent. However, several disadvantages are associated with such emulsions. They are usually much more viscous than acid solutions thus high pumping pressures are needed. Also, the stability of the emulsions are temperature sensitive; such emulsions are hard to prepare; such emulsions may block the pores of the formations and the like.

In another method an anionic surfactant which renders the surface of a formation oil-wet is dispersed into an acidizing formulation, e.g. US. Pat. No. 3,319,714. However, it has been discovered that these types of surfactants are not effective in aqueous solutions containing higher concentrations of acids, e.g. per cent or more HCl solutions.

SUMMARY OF THE INVENTION An aqueous acidizing acid solution is prepared containing a cationic surfactant which in the presence of said acid renders oil containing formations oil-wet. A sufficient amount of said surfactant is employed to substantially increase the reaction time of the acid acting on the formation.

DETAILED DESCRIPTION OF THE INVENTION Surfactants which can be employed in the practice of the present invention include C to C primary fatty amines or mixtures thereof, corresponding to the formula RNH wherein the R group comprises a C to C alkyl group. Specific surfactants which can be employed include, for example, cocamine, dodecyl amine, tetradecylamine, decylamine, octyl amine, etc.

The reaction time of any aqueous acidizing acid solution for calcareous formations, e. g. limestone, dolomite and other formations, can be increased by incorporating into the acid a sufficient quantity of the above-identified surfactant. There appears to be no critical quantity and the amount employed will depend on such factors as desired increase in reaction time, economic considerations and the like. Suitable results can be obtained when as little as about 0.1 per cent by weight of the surfactant is employed. Economic considerations generally dictate a maximum amount of about 10 per cent by weight of surfactant in the acidizing formula tions.

Acidizing acids which can be employed include HCL, HF, formic acid, acetic acid, sulfamic acid, various mixtures thereof and other acids which are compatible with the specific surfactants employed. The acid solutions can contain up to about 30 per centby weight or more of the acid. The surfactants of the present invention are especially useful in solutions containing more 2 than about 15 per cent by weight of an acidizing acid, e.g. HCl.

The surfactants which are useful in the practice of the invention, e.g. amines, are difficult to disperse into aqueous acidizing formulations. Thus it is often desirous, especially when batch mixing procedures are employed to employ, with the surfactant, a dispersing agent (e. g. a surface active agent) such as a quaternary amine, e. g. lauryl dimethyl benzyl ammonium chloride or octyl dimethyl ammonium chloride and the like to aid in dispersing the surfactant into the aqueous solution.

If the cationic surfactant is added to a moving stream of the acid formulation the dispersing agent may be dis pensed with.

It has been found, in contrast to the teachings of US. Pat. No. 3,319,714, col. 4, lines 54-60, that certain cationic surfactants have as good a retarding effect in acidic formulations, and in some circumstances a better retarding effect than do certain anionic surfactants. The reason for this result is not known. However, the present invention now makes it possible to employ cationic surfactants in these acid solutions.

The method and composition of the present invention is practiced using standard acidizing equipment and procedures well known in the art. The composition and method can be employed in matrix and fracturing acidizing techniques. Further, the composition may contain other constituents, e.g. freezing point depressants, corrosion inhibitors, etc., well known to the art.

EXAMPLE l A series of tests were performed to determine the ability of a particular surfactant to form a tenacious oil film on a limestone surface, i.e., render the surface oilwet. Over 400 surfactants were tested. Two per cent by volume of a specific surfactant was mixed into kerosene. A 1 inch by 1 inch by inch limestone coupon was then soaked in the kerosene surfactant solution for 1 minute. The coupon was then removed from the kerosene surfactant solution and placed in a 15 per cent hydrochloric acid solution. The surface of the coupon was observed to determine the length of time before the coupon started to react with the HCl solution. Those kerosene surfactant solutions which produced a 5 second or longer delay in the time required for acid reaction over the entire surface were tested further as follows.

The second stage testing of various surfactants as retarders involved the determination of actual reaction rates in 15 per cent HCl under 1,000 psi pressure. Tests were performed under static conditions using a high pressure reaction rate cell maintained at room temperature. Reaction rates were run on 1 inch X 1 inch X A inch Bedford limestone coupons which had previously been weighed. The acid solution to be tested was composed of 90 ml of 15 per cent HCl, 0.4 ml of a known corrosion inhibitor, 10 ml kerosene and 2 ml of a specific surfactant. The coupon and acid solution were placed in the cell and the cell pressured, with nitrogen, to 1,000 psi. The test was begun by inverting the cell,

I thus exposing the coupon to the acid. At the end of the test period (5 minutes), the cell was again inverted, the pressure released, and the coupon removed, dried and weighed. Reaction rates were then calculated. Results using some of the surfactants tested are set forth in the following Table I.

TABLE 1 reaction rate of the acid. The results of these tests are set forth in the following Table 111. Reaction Rate Surfactant (lb/fF/scc) X 10 TABLE 111 None 2.54 5 Percent of Cocamine Reaction Rate C alkyl sulfonate .16 In 28% HCl (lb/ft /sec) X Dodecyl benzene sulfonic acid .17 Amine salt of alkyl benzene .19 1 -22 sulfonic acid 0.5 .94 Cocamine .27 0.25 .19 Amine alkyl aryl sulfonate .08 Alkyl sulfonate .16 10 Anionic sulfate salt .1 1 Calcium sulfonate ,14 Lauryl sulfate 1 |4 Dimethyl cocamine salt of ortho: .28 3

i ",{;f.,1? Various other amines were tested as retarders in 15 and 28 percent l-lCl by the test procedure described in Those surfactants which showed some ability to retard 15 percent l-lCl (i.e., showed a reaction rate of less than about 0.002 lbs. per sq. ft. per sec.) were next tested employing a 28 percent HCl solution. Test conditions were the same as employed in the second stage test described above, except that 28 percent HCl was used. Three surfactants, primary cocamine, lauryl sulfate and dimethyl cocamine salt of orthophosphoric acid neutralized with sodium hydroxide showed reaction rates of 0.18; 0.26 and 0.66 1bs/ft /sec X 10 respectively. The next best surfactant was dodecyl benzene sulfonic acid 1.12 1bs/ft /sec X 10" and a linear alkyl aryl sulfonic acid 1.76 lbs/ft /sec X 10 These latter two rates are too high to be considered of practical importance.

The three surfactants listed above which demonstrated rates of 0.66 lbs/ft /sec X 10' or less were next tested under conditions of reduced surfactant and kerosene concentration. Test conditions were the same as in previous tests except as noted in the following Table 11. The reduction in surfactant and kerosene concentration greatly reduced the degree of retardation of the acid solution, i.e., the reaction rate was increased. Of 40 the three surfactants tested, primary cocamine showed the greatest retarding efiect at the lower concentrations employed in this test. The results of these tests are set forth in the following Table 11.

A series of retarding tests were performed employing cocamine in the pressurized cell described in Example 1. In this series of tests the coupon was saturated with kerosene prior to the test. No kerosene was added to 65 the acid solution.

The amount of primary cocamine employed in 28 percent HCl was varied to determine the effect on the Example 2. The results of these tests are set forth in the following Table IV.

TABLE IV Percent Reaction Rate by Wt. HCl Conc (lb/ft /sec) Amine in HCl Per Cent X 10 None 15 1.59 None 28 1.62 Hexyl amine 0.5 15 1.87 Hexyl amine 0.5 28 1.86 Octyl amine 0.5 15 1.54 Octyl amine 0.5 28 .88 Tctradecylamine 0.5 15 1.12 Tetradecylamine 0.5 28 1.95 Hexadecylamine 0.5 15 1.98 Hexadecylamine 0.5 28 1.76 Octadecyl amine 0.5 28 1.67 Cocamine 0.5 15 .22 Cocamine 0.5 28 .40 Oleyl amine 0.5 28 1.67 Cotton seed amine 0.5 28 1.60 Tallow amine 0.5 28 2.72 Dicocamine 0.5 28 1.61 Dimethyl cocamine 0.5 28 5.1 1

EXAMPLE 4 45.5 cocamine 9.0 lauryl dimethyl benzyl ammonium chloride (dispersant) 16.0 methyl alcohol 17.0 H O 12.5 acetic acid Reaction rate tests were performed in a pressurized cell in the manner described in Example 1 employing 28 per cent HCl and 20 per cent HCl containing 1.1 per cent by volume of the above defined formulation. The reaction rate determined for the 28 per cent l-lCl solution was 10 (1b/ft /sec) X 10* and with 1.1 per cent by volume of the above formulation the reaction rate was 2.0 (1b/ft /sec) X 10 The 20 per cent l-lCl solution had a reaction rate of 1 1.0 (lb/ft /sec) X 10" and the reaction rate of the 20 per cent HCl containing 1.1 per cent by volume of the above formulation was 0.6 (lb/ft /sec) X 10 What is claimed is: 1. A composition for acidizing a subterranean formation which comprises:

an aqueous acidizing acid solution for said formation and an effective amount of a cationic surfactant in said solution to reduce the normal reaction rate of said acidizing solution on said formation, said cationic surfactant consisting of a alkyl C to C primary amine characterized as rendering the formation surface oil-wet.

2. The composition of claim 1 wherein said amine is dodecyl amine.

3. The composition of claim 1 including in addition a surface active agent which aids in dispersing said cationic surfactant in said acid solution.

4. The composition of claim 1 including in addition a minor quantity of oil dispersed in said composition.

5. A method of acidizing an oil containing subterranean formation with an acidizing acid solution which comprises:

contacting the subterranean formation with an acid izing acid solution containing dispersed therein an effective amount of a cationic surfactant consisting of C to C primary amine to increase the normal reaction time of said acidizing acid solution with said formation, said cationic surfactant characterized as, in the presence of said acid, rendering oil containing formations oil-wet.

6. The method of claim 5 wherein said amine is dodecyl amine.

7. The method of claim6 wherein the subterranean formation comprises a calcareous material.

8. The method of claim 6 wherein said acidizing acid solution contains in addition a surface active agent 6 which aids in dispersing said cationic surfactant in said acidizing solution.

9. The method of claim 6 wherein said acidizing acid is l-lCl.

10. The composition of claim 1 wherein said acid is HCl.

11. The composition of claim 10 wherein said amine is dodecyl amine.

12. The method of claim 6 wherein said acidizing acid solution contains in addition a minor quantity of oil dispersed in said solution.

13. The method of claim 6 wherein the formation contains limestone.

14. The composition of claim 1 wherein said cationic surfactant comprises cocoamine.

15. The method of claim 6 wherein said cationic surfactant comprises cocoamine.

16. The composition of claim 1 wherein said acidizing solution contains greater than 15 per cent of said acid.

17. The composition of claim 16 wherein said acid is HCl.

18. The method of claim 6 wherein said acidizing solution contains greater than 15 per cent by weight of said acid.

19. The method of claim 18 wherein said acid is HCl.

20. The method of claim 18 wherein said amine is dodecyl amine.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,917,536

DATED November 4, 1975 INVENTOR(S) Curtis W. Crowe It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In column 4, line 59, delete "10 and insert -lO In column 5, Claim 7, line 1, delete "6" and insert 5.

In column 5, Claim 8, line 1, delete "6" and insert 5.

In column 6, Claim 9, line I, delete "6" and insert 5.

In column 6, Claim 12, line I, delete "6" and insert 5.

In column 6, Claim 13, line 1, delete "6" and insert 5.

In column 6, Claim 15, line I, delete "6" and insert 5.

In column 6, Claim 18, line I, delete "6" and insert 5.

Signed and Sealed this E sixth Of April 1976 Attest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner ofParenIs and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENTNO. 3,917,536

DATED November 4, 1975 |NVENTOR(S) Curtis W. Crowe It is certified that error appears in the ab0veidentified patent and that said Letters Patent are hereby corrected as shown below:

In column 4, line 59, delete "10 and insert -l0 In column 5, Claim 7, line 1, delete "6" and insert 5-.

In column 5, Claim 8, line I, delete "6" and insert 5. In column 6, Claim 9, line I, delete "6" and insert -5-.

In column 6, Claim 12, line 1, delete "6" and insert -5-.

. In column 6, Claim 13, line I, delete "6" and insert --5.

In column 6, Claim 15, line I, delete "6" and insert --5--.

In column 6, Claim 18, line I, delete "6" and insert --5 Signed and Scaled this sixth Day of Aprill976 [SEAL] Attest.

C. gin-SON C. MARSHALL DANN "'8 ff (ummissl'oner ufParents and Trademarks 

1. A COMPOSITION FOR ACIDIZING A SUBTERRANEAN FORMATION WHICH COMPRISES: AN AQUEOUS ACIDIZING ACID SOLUTION FOR SAID FORMATION AND A EFFECTIVE AMOUNT OF A CATIONIC SURFACTANT IN SAID SOLUTION TO REDUCE THE NORMAL REACTION RATE OF SAID ACIDIZING SOLUTION ON SAID FORMATION, SAID CARIONIC SURFACTANT CONSISTING OF A ALKYL C8 TO C18 PRIMARY AMINE CHARACTERIZED AS RENDERING THE FORMATION SURFACE OIL-WET.
 2. The composition of claim 1 wherein said amine is dodecyl amine.
 3. The composition of claim 1 including in addition a surface active agent which aids in dispersing said cationic surfactant in said acid solution.
 4. The composition of claim 1 including in addition a minor quantity of oil dispersed in said composition.
 5. A method of acidizing an oil containing subterranean formation with an acidizing acid solution which comprises: contacting the subterranean formation with an acidizing acid solution containing dispersed therein an effective amount of a cationic surfactant consisting of C8 to C18 primary amine to increase the normal reaction time of said acidizing acid solution with said formation, said cationic surfactant characterized as, in the presence of said acid, rendering oil containing formations oil-wet.
 6. The method of claim 5 wherein said amine is dodecyl amine.
 7. The method of claim 6 wherein the subterranean formation comprises a calcareous material.
 8. The method of claim 6 wherein said acidizing acid solution contains in addition a surface active agent which aids in dispersing said cationic surfactant in said acidizing solution.
 9. The method of claim 6 wherein said acidizing acid is HCl.
 10. The composition of claim 1 wherein said acid is HCl.
 11. The composition of claim 10 wherein said amine is dodecyl amine.
 12. The method of claim 6 wherein said acidizing acid solution contains in addition a minor quantity of oil dispersed in said solution.
 13. The method of claim 6 wherein the formation contains limestone.
 14. The composition of claim 1 wherein said cationic surfactant comprises cocoamine.
 15. The method of claim 6 wherein said cationic surfactant comprises cocoamine.
 16. The composition of claim 1 wherein said acidizing solution contains greater than 15 per cent of said acid.
 17. The composition of claim 16 wherein said acid is HCl.
 18. The method of claim 6 wherein said acidizing solution contains greater than 15 per cent by weight of said acid.
 19. The method of claim 18 wherein said acid is HCl.
 20. The method of claim 18 wherein said amine is dodecyl amine. 